Quaternary compounds



QUATERNARY COMPOUNDS John P. Conbere and Firmin P. Reed, Providence, R. I., assignors to Arnold, Hoifman & Co., Incorporated, Providence, R. I., a corporation of Rhode Island No Drawing. Application May 19, 1955 Serial No. 509,676

16 Claims. (Cl. 260-895) The present invention relates to new quaternary ammomum salts of certain amino ethers of polyglycol esters of acrylic acids, polymers of such esters and textiles treated with such polymers to impart antistatic properties thereto.

One disadvantage of textile fibers and particularly of fabrics prepared from synthetic hydrophobic materials, and of all textile fibers treated with conventional resin finishes, is that they tend to develop a static electrical charge. This charge is objectionable during the manufacture of the textile and in the finished garment. During manufacture the static charge on the fibers or fabric interferes with their convenient handling during spinning, reeling, weaving and the like. Finished articles which are designed to drape like cotton or wool articles fail to do so properly due to their electrostatic charge and often cling uncomfortably to the wearer. Furthermore, such textiles tend to collect dust and lint, and the electric discharge itself is bothersome.

Many treating agents have been proposed to impart anti-static effects to textiles of this type. However, none of the proposed agents is entirely satisfactory, either because of their ineifectiveness or their lack of resistance to washing and dry cleaning. Many of these anti-static agents are efiectively transferred to the textile materials only with great difiiculty.

It is an object of this invention to prepare new quaternary monomers.

A further object is to prepare new quaternary polymers.

Another object is to provide textile fibers and fabrics with a coating of an anti-static agent.

An additional object is to apply an anti-static agent to a textile material in a simple and economical manner.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only,

. since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that-these objects can be attained through the preparation and polymerization of new monomers of quaternary ammonium salts of dialkyl amino alkyl ethers of ethylene glycol and polyethylene glycol as more fully defined below. a

The polymeric quaternary ammonium esters of the glycol derivatives possess the unique characteristic of imparting antistatic properties to textile fabrics. The polymers can be fixed to the fabrics by after treatment with a soap of a fat acid, long chain alkyl and alkenyl sulfate salts, aralkyl sulfate salts or alkyl, aralkyl or alkaryl sulfonate salts. The polymeric products of the present invention and the long chain anions from the aftertreatment form a water insoluble adduct which resists removal 2,824,861 i atented Feb. 25,

c EC

wherein R is hydrogen or methyl, R is an alkyl group containing one to four carbon atoms, R is an alkyl group containing one to four carbon atoms or R and R can be together joined to form with the nitrogen atom a heterocyclic ring, the hetero atoms of said ring being nitrogentor nitrogen and oxygen, e. g., a piperidine, a piperazine or morpholine ring, R, is methyl or ethyl, n is an integer from one to five inclusive, z is an integer from two to four inclusive and X is an anion.

Typical examples of compounds coming within the ,above formula are the N-rnethyl methyl sulfate of the methacrylateester of S-diethylaminoethyl ether of ethyl- -ene glycol, N-methyl p-toluene sulfonate of the methacrylate ester of firdiethylaminoethyl aminoethyl ether of -ethylene glycol, N-ethyl ethyl sulfate of the methacrylate "ester of B-diethylaminoethyl ether of ethylene glycol, N- .ethyl bromide of. the methacrylate ester of p-diethyl- Iaminoethylether of ethylene glycol, N-methyl methyl sul- /fate of the methacrylate ester of fi-diethylaminoethyl ether .Vof diethyleneglycol, .N-methyl methyl sulfate of the methacrylate ester of B-diethylaminoethyl ether of tri- :ethylene glycol, N-methyl methyl sulfate of the methacrylate ester of the 8-diethylaminoethyl ether of tetraethylene glycol, N-methyl methyl sulfate of the methacry- 'late ester of B-diethylaminoethyl ether of pentaethylene glycol, N-methyl methyl sulfate of the acrylate ester of s-diethylaminoethyl ether of ethylene glycol, N-rnethly methyl sulfate of the methacrylate ester of B-dimethylamino ethyl ether of ethylene glycol, N-methyl methyl sulfate of the methacrylate ester of B-dibutylaminoethyl 40 ether of ethylene glycol, N-methyl methyl sulfate of the methacrylate ester of [8(1-PlP6IldlI10) ethyl ether of ethylene glycol, N-methyl methyl sulfate of the methacrylate .ester of ti-diethylaminobutyl ether of ethylene glycol, N- .methyl methyl sulfate of the methacrylate ester of ,8- methyl butylaminoethyl ether of ethylene glycol, N- methyl methyl sulfate of the methacrylate ester of 18(1- .morpholino) ethyl ether of ethylene glycol.

. In the formula X is preferably the anion of a strong acid and more specifically is a halide such as chloride.

50 bromide or iodide or is the anion of a strong sulfur acid,

.e. g., sulfate, methyl sulfate, ethyl sulfate, and other alkane sulfates, p-toluene sulfonate, butyl sulfate, mxylene sulfonate, benzene sulfonate and other aryl sulfonates.

The polymerization of the monomers can be carried 'out in the presence of conventional free radical type catalysts in aqueous media. Typical catalysts include iperoxy compounds such as ammonium persulfate, benzoyl peroxide, lauroxyl peroxide, acetyl peroxide, hydrogen peroxide, sodium persulfate, potassium persulfate, azo compounds having the azo, N=N-, group acyclic joined to discrete non-aromatic carbons at least one of which is a tertiary carbon atom in turn joined to a carbon atom whose remaining valences are satisfied by oxygen and/or nitrogen (as in Hunter, U. S. Patent 2,471,959) such asazodiisobutyronitrile, etc. The amount of catalyst empolyed is generally small, e. g., 0.0l5% by Weight of the polymerizable monomer. The monomers can be homopolymerized or copolymerized with each other or other copolymerizable monomers.

The'monomeric quaternary ammonium salts are soluble in water and the polymers are obtained in the form,

; without drying is of an aqueous syrup. The syrup can be dried to give a semi-solid sticky mass which redissolves in water only with difiiculty. Preferably, however, the aqueous syrup employed directly to treat the textile fiber or fabric.

Polymerization cancarriedoutjby treating an aqueous monomer solution with'the catalyst or by adding monomertot a solution of the desired catalyst; ,The polymerization'can be carried out atfrom "about 4 C. to. 100 Y I In order to prevent unduly high polymerization, variousconventional polymerization inhibitors, such as arom a tic amines andalkylphenols, can be present both during j the-r formation of the monomerand"fortnation"of"the polymer. 'On'the other hand; it is'possible by us'ing'very small amounts of catalystand by eliminating the inhibitor to produce more highly polymeric productsin the The formiof a r-resin gel. anion'exchange resins.-

However, the preferred materials are the aqueous syrups which can be applied as such as antistatic agents resin gels' can be usedias to textilermaterials, including fibers. yarns, threads and t fabrics, formed from nylon (polymeric hexamethylene adipamide, epsilon caprolactam polymer, and other synthetic linear superpolyamides, etc.),'cellul ose acetate, and other ,cellulose esters, polyacrylonitrile, polyethylene or sulfur containing detergent sojas to'pic k up 0.75%

to .90% of 'the'latter, and is then'dried again to give the final antistatic material. a

As the soap or other detergent, there'ca n be used watersoluble'salts such as sodium stearate, potassium stearate, ammonium stearate, sodiumoleate, potassium 'oleate, the potassium soap of coconut fatty acids, sodium 'laurate, sodium oleyl' sulfate, sodium octyl sulfate, sodium 'hexadecenyl sulfate, sodium dodecyl sulfate, po}

tassium dodecyl sulfate, sodium lorol sulfate (this is a *mixture of the sodium salts of alkyl sulfates in which V terephthalate, polyvinylidene chloride, and other fabrics t which tend tojaccumulate static electric charges. 1 a In, the preferred method of operation, the .fabric is padded throught a dilute aqueous solution of the lquaternary ammoniumpolymer so as to pick up about 0.l% t0 1.9% of the quaternary compound. The fabric is'framedried and then rinsed with'a dilute solution of the soap the-alkyl groups-havefromf10 to 14 carbon atoms with an average of aroundjlZ carbon atoms), N-diethylcycld- 'hexyl ammonium dodecyl sulfate, sodium salt of the sulfates of mixed dodecyl-tetradecylalcohols condensed with "about one mol of ethylene: oxide, ammonium dodecyl sulfate, sodium cetyl sulfate, potassium cetyl'sulfate, sodium saltof mixed cm c "a1ken 1 sulfates (alcohols derived from the sodium reduction of sperm oil), sodium,

salt of the sulfate of octadecenylalcohol condensed with about one mol of ethylene oxide, sodium dodecane sul fonate, potassium octadecane sulfonate, sodium alkyl benzene sulfouatesv wherein the alkyl group has an average chain length of'lO, 14 or 18 carbon atoms, e. g.,-sodium .dodecylbenzene sulfonate, sodium I phenyl hexane 'sulfonate, sodium octyl-phenylbutane"sulfonate, salts of alkylsulfosuccinatesye g.,"sodiurn dioctylsulfosuccinate and sodium dihexylsulfosuccinate arylalkyl ether sulfonates; e. g., the sodium salt of'the octylphenyl ether of hydroxyethoxy,ethanesulfonicacid, sodium monob'utyl 'phenylphenol sulfonate,"' etc. 'In j general; the detergent should have at least eight carbon atoms.

The starting aminoethers for preparing the new quaternary compounds can be prepared by conventional proc essesfin the art, a preferred m'ethod is that 'described'by Headle et al inJour. Amer."Chem.'lSoc.,'vol.f55, pages 1O66.1068.j j

v For convenience, the-nomenclature system throughout the specification and elaimsiisjbased on a glycol ether system. It is evident that then-new compounds are ethersa do hel rs ea Palm e narys g ouhi s am m aumo spr aaqxiq an -1 t.

:ua .trs tsdin he s m man er. ass ssaib q. message a first polymeric acrylic acid esters having both a quaternary ammonium group and an ether group which have proven to be efiective antistatic agents.

The dialkylaminoalkylether of the alkylene glycol .or the pt(1-piperidino) alkyl ether of the alkylene glycol is then reacted withmethyl acrylateor methyl methacrylate or 7 a phosphate, trialkyl phosphites,-e.' g., tricthyl phosphite,' alkyl esters of'alkyl or aryl sulfonic acids, e. g., methyl hexane sulfonate, methyl; p-toluene sulfonate, ethyl ptoluene sulfonate,.ethy l benzene sulf onate, etc, There,-

rsulting quaternary ammonium salts are soluble'in water, 'fj Inthe following examples and throughout the specifica tion and claims, all parts are parts by weight unless otherwise indicated. o

-P E RA QN. RT E' FER IAR ETHERS 015 THE At'KY ENe'o Yco s {The esters formed'l'in ExamplesI throughf are water .insolublea" 5: j i

Q ixarirplll V Methacrylate ester of ip-diethylaminoethyl ether 7 of ethylene glycol. a I

' A flask fitted'withjarcopper -gauze packed fi'actionating column with a distillinguheadj arranged for controlled reflux was charged with 161, g.,ffif-diethylaminoethyl ether of ethylene glycol, 30 g'. phenyl p naphthylamin'e'ffil g; alupminum isopropoxide and 4005ml'; methyl methafcrylate- "The mixture was heated undennitrogen, u'ntil'it-refluxed,

and the methanol formed frojm the methyl methacrylate' 'After the theoretical iby ester interchange distilled, 7

amount of methanol had been collected, the charge .was

cooled and. 1 50 ml.of concentrated hydrochloric acid. 500 ml. of waterwas added with stirring. The aqueous layer Was extracted with three500 ml. portions of ether, the emulsions formed being broken with saturated'sodium' chloride solution, The aqueous layer was made alkaline with g. sodium hydroxide dissolved in 300 m1. of'watera One gram of phenyl'fi naphthylamine.wasadded, and the mixture extractedwith1 three; 5 00 ml. portions of ether.

The' ether layers from; the alkaline extraction were com- "bined,'wa shed with 75 -ml.- of saturatedsodium chloride solution, dried over sodium sulfate and the. solvent'disjtilled. The residue was; distilled at reduced pressure to a 'yield the producnB. P. l2l 5 C, at 4 mm., 7155.1.4470;

' Analysis.-' .Calcd for C H NQ N, 6.12. 7 Found: N, ff". I l 1 iTE Q P I.

' 'Methacrylate ester of ethylene glycol;

A charge 015.2705. g. fi:diethylaminoethylether 6r diethyl-o 'enetglycol, 30 g.jphenyl fi-naphthyla'mine, 20 g. aluminum 'isopropoxide'and400 ml. methyl methacr'ylate was treated I "inothe same manner as described 'in'Example' I. The prod mile 111 a illvlethacrylate Iediethylaminoethylether. of

ethyleneiglycol; t I a t Aibhq t o 7 ethylene. lycoL I lQ g. phenylp-naphthylamine, 20 g. am-

B -diethylaminoethyl ether: of di-.

qr; 249 "e-diethylanfinoethyl ether oist;

methyl methacrylate gage-em i I. The product boiled at'.114-130 C. at 0.1 mm., a 1.4589.

Analysia-Calcd. for 'C H NO N, 4.42. Found: N, 4.55.

Example IV Methacrylate esterof fl-diethylaminoethylether of tetraethylene glycol.

A solution of 29.3 g. of fi-diethylaminoethyl ether of tetraethylene glycol in 100 ml. benzene. was dried by azeotropic distillation. The solution was cooled and 13 g. of methacrylyl chloride slowly added, maintaining the temperature .at less than 40 C. The reaction mixture was allowed to stand over-night at room temperature. After shaking this mixture with ml. 6 N sodium hydroxide, the benzene layer was washed with sodium chloride solution and dried over sodium sulfate. The solvent was distilled at reduced pressure to yield the product as a heavy syrup.

Example V Methacrylate ester of fl-diethylaminoethyl ether of pentaethylene glycol.

A solution of 67 g. of /3diethylaminoethyl ether of pentaethylene glycol was treated with 24 g. of methacrylyl chloride in the same manner as described in Example IV. The product was obtained as a heavy syrup.

Example VI Acrylate ester of B-diethylaminoethyl ether of ethylene glycol.

Aeharge. of 161 g. fi-diethylaminoethyl ether of ethylene glycol, 400 ml. benzene, 17 g. Ionol (2,6 ditertiary butyl-4-methyl phenol) and 72g. methyl acrylate was heated in a flask fitted with a copper gauze packed fractionating column and a distilling head arranged for partial take-oil, until the head temperature reached 80 C. The charge was cooled to 80 C. and a solution of 0.3 g. sodium hydroxide in 6.6 ml. methanol added over a period of two hours with continual distillation of the benzene-methanol azeotrope. The distillation was continued until the head temperature reached 79 C. and remained there under total reflux. The charge was cooled and shaken with 200 ml. of water. After separating the layers, the organic layer was driedwith sodium sulfate and the solvent distilled. The residue was distilled to yield the product, B. P; 1124114 C. at 5 mm. The product had a tendency to polymerize in the distillation receiver.

Example VII Methacrylate ester of fi-dimethylaminoethyl ether of ethylene glycol.

A solution of 66.5 g. of fi-dimethylaminoethyl ether of ethylene glycol in 100 ml. benzene was treated with 52 g. methacrylyl chloride in the same manner as described in Example IV. The product was distilled at reduced pressure, B. P. 105-108" C. at 4 mm.

Example VIII Methacrylate ester of fl-dibutylaminoethyl ether of ethylene glycol.

A solution of 7.8 g. dibutylaminoethyl ether of ethylene glycol in 25 ml. benzene was treated with 4.0 g. methacrylyl chloride in the same manner. as described in Example IV. The product was a syrup.

Example IX Methacrylate ester of S(1-piperidino)ethyl ether of ethylene glycol.

A solution of 17.3 g. ;3(1-piperidino)ethyl" ether of ethylene glycol in 50 ml. benzene was treated with 12 g. methacrylyl chloride in the same manner as described in Example IV. The product was isolated as a viscous liquid.

The quaternary ammonium compounds formed inExamples X through XXI are all water soluble.

a QUATERNARY AMMONIUM COMPOUNDS Example X N-methyl methylsulfate of the methacrylate ester of fi-diethylaminoethyl ether of ethylene glycol.

To 76.3 g. of the methacrylate ester of B-diethylaminoethyl ether of ethylene glycol containing 1% Topanol A (2,4 dimethyl-6-tertiary butyl phenol) was slowly added 42. g. dimethyl sulfate with vigorous stirring. The temperature was maintained at 5055 C. during the addition of the first two-thirds of the dimethyl sulfate and at 55- 60 C. during the addition of the final third. The reaction mixture was heated at 60 C. for ten minutes after the .addition was completed. The product was obtained as a clear viscous liquid.

Analysis.Calcd. for C H NO S: N, 3.95 S, 9.02. Found: N, 4.02; S, 9.18.

Example XI N-methyl p-toluene-sull'onate of the methacrylate ester of fi-diethylaminoethyl ether of ethylene glycol.

Methyl .p-toluenesulfonate (9.3 g.) was slowly added to 11.45 .g. of the methacrylate ester of p-diethylaminoethyl ether of ethylene glycol which was stirred and maintained at 50-60 C. After the addition was completed, the reaction mixture was heated for ten minutes at 50-60 C. Analysis.Calcd. for C H NO S: N, 3.38; S, 7.73. Found: N, 3.41; S, 7.7.3.

Example XII N-ethyl ethylsulfate of the methacrylate ester of p-diethylaminoethyl ether of ethylene glycol.

11.5 g. of the methacrylate ester of fl-diethylaminoethyl ether of ethylene glycol was treated with 7.7 g. diethyl sulfate by the same procedure as described in Example IX. The product was obtained as a viscous liquid which was soluble in water.

Example XIII N ethyl bromide of the methacrylate ester of ,B-diethylaminoethyl ether of ethylene glycol.

A solution of 15 g. ethyl bromide and 25.7 g. of the methacrylate ester of ,B-diethylaminoethyl ether of ethylene glycol in 25 ml. of anhydrous ether was allowed to stand at room temperature for two weeks. The ether layer was decanted and the lower syrupy layer triturated with anhydrous ether. The occluded solvent was removed under reduced pressure. The product was obtained as a viscous liquid.

Example XIV N-methyl methylsulfate of the methacrylate ester of fl-diethylaminoethyl ether of diethylene glycol;

109.2 g. of the methacrylate ester of .B-diethylaminoethyl ether of diethylene glycol was treated with 50.5 g. dimethyl sulfate by the same procedure as described in Example IX. The product was obtained as a clear viscous liquid which was soluble in water.

Example XV N-m-ethyl methylsulfate of the methacrylate ester of B-diethylaminoethyl ether of triethylene glycol.-

106 g. of the methacrylate ester of fl-diethylamino ethyl ether of triethylene glycol was treated with 42.5 g. dimethyl sulfate by the same procedure as described in Example lX. The product was obtained as a viscous liquid which was soluble in water.

Example XVI N-methyl methylsulfate of the methacrylate. ester of the fi-diethylaminoethyl ether of tetraethylene glycol.

33.2 g. of the methacrylate ester of ,8 diethylaminoethyl ether of tetraethylene glycol was treated with 11.6 g'. dimethylsulfate by the same procedurepas describedin Example IX. The. product was obtained as a viscous liquid which was soluble in water.

f1" 1.. 1 (Example XVII I; N-methyl methylsulfate of. the methacrylate ester of :fl-diethylaminoethylether of. pentaethyleneglycol.

- V 60' g. of tlie m'ethacrylate ester of fi diethylamiiioethyl ether. of pentaethylene glycol was treated .witli;18.7- g.

dimethylsulfate by the same. procedure as ldes'cribedin Example IX. .The -vi's'cou's product was; soluble; inwater.

: .ExampleX V lll. I;

ethyl ether of ethylene glycol was treated with 10.9 g.

dimethylsulfate by the procedure described in EXampleIX "to yielda viscous liquid which was soluble in water- 'Erarr pl eXX' 1 hl-methylsulfate 5f the methac rylatef esfer of B-:dibutyl-' aminoethyl ether of ethylene glycol. r

A Solution of 8.8 g.1'of'.themethacrylate ester of B- dibutylaminoethyl ether of ethyleneglycol in v.10..ml. benzene was heated to. reflux andtreatedjwith 3.9lg. dimethyl sulfate. The reaction mixture was refluxed for thirtyfminutes after the additionwa's completed. The

solvent was removed at reduced pressure toyield 'a water soluble syrup. v l .1 1 V Examp'leXXlf N-methyl methylsulfate of themethacrylate ester of fl(1-piperidino)ethyl etherfof ethylene glycol.

' 24.1 gfofthe methacrylate ester of fi(1-piperidin0)- ethyl ether of ethylenelglycol was treated with 12.6 g.

.Polymer-of N.-methyl methylSulfate.pf methacrylate ester "of fi diethyla'minoethyl ether of diethyl'ne "glyc'ol'. v

A solution of 149 .g. pf the monomeric quaternary ammonium salt in 333 ml. water was treated with a solution.of-1.5. g.f: ammonium; pier'sulfate. 111715. ml... watril by l the procedure described in Example. XXII to-.yield:.a

polymeric. solution with a greater vis'cosity than the monomeric solution.s;:*i r

Y 'ExampleXXVfl' v V Polymer of 'N-methyl methylsulfateof the methacrylate ester "of p diethylaminoethyl jether of 'triethylene glycol. A solution; of 16.1 gsof the monomeric. quaternary ammonium salt in 35 ml. water was treated. with 0.116

g. ammonium persulfate in 31ml; water by the procedure describedin. Example XXII to yield a polymeric solution with greater viscositythan'the initial solution; j

Example i i f Polymer of N-methylmethylsulfate of the methac rylat ester of ,B-diethylaminoethyl-ether of "tetraethylene glycol. 1 A

A solution of 21 ga or the monomericquaternary ammonium salt in 45 ml. of water wastreated with a solution of 0.2 g. ammonium persulfate in 3 ml. water by V the procedure described in Example XXII. A more'vis- Bolymer offN-methylmethylsulfate ofthe methacrylate. ester of fl-diethylaminoethyl ethe'r of pentaethylene glycous solution resulted.after theyreaction had occurred.

, I Example XXVII col."

dimethylsulfate by the procedure described inEXample IX to yield a viscous liquid which was soluble in water.

1' x e X" .1; N-methyl methylsulfate of the methacrylate ester of -y-dimethylaminopropyl ether of .diethylene glycol.

Dimethyl sulfate (100 g.) wasadded slowly to a refluxing solution of206 g. ofthe methacrylateesteriof 'ydimetliylaminopropyl etherof dithylene glycol in 259 1g. benzene during thirty minutes. The mixture was stirred "at the reflux temperature for an additional thirty minutes. ,The reaction mixture was cooled tol C. and 650ml. water added. The whole was stirred for fifteen minutes, transferred to a separatory funnel/and the layers allowed to separate. 7

quaternary ammonium compound... 7

PQLYMERS The polymers described in each of Examples XXIII through XXXV were obtained in the form of aqueous solutions and could be driedto sticky semi-solid masses which redissolved in water only with difficulty.

. I Example XXIII; v

Polymer of N-methyl methylsulfate ofmethacrylate ester of ,S-diethylaminoethyl. ether of ethylene glycol.

Nitrogen was bubbled througha solution of 104.9 g.

of the monomeric quaternary ammonium salt in 230ml.

water-.1 The solution was heated to 95 Cgand a solution of 1.04 g; ammonium persulfate in 15 waterlslowly 'added thereto. The temperature spontaneously rose to 98 C.'and the mixturewas maintained at 90295" C. for

the reaction. 7

The aqueous layer contained thedesired j A solution'of 14.0' g. the monomeric quaternary ammonium salt in 50 m1. of water was treated with a solution of 0.14 gpammoniumpersulfate in 6. ml. of" water 'by the procedure described in --EXample XXII ito yield a more viscous prodrict V l 7 V V Exdmpl xX Vllif f Polymer of N-methyl p-toluenesulfonate of themethacrylate ester of fi-diethylaminoethyl ether'of ethylene glyl col. A solution-of 14.0 g. of the monomeric quaternary ammonium salt in 31ml. water was treated 'witha solution of 0.14 'g. ammonium persulfate in 1.7 ml. water as described in Example ml; The resultantfsolutio'n ofthe.

polymer was thick and syrupy.

Example XXIX Polymer. of- N-ethyl ethyls'ulfate of the methacrylate ester of fl-diethylaminoethyl ether of ethylene glycol.

A solutionof 15.3- g. of the monomeric quaternary ammonium salt in"33.7 ml. water was' treated with a solution of 0.15 g. ammonium persulfate in- 2 ml. water as described in Example XXII. The product was'obtained as a viscous solution. r r 7 Example XXX Polymer of'N-ethyl-bromide of the methacrylate ester o f p-diethylaminoethyl ether of ethylene glycol;

A solutionof 7.5 g. of the monomeric quaternary ammonium salt in 17 ml. water was treated with 0.075 g'. ammoniumpersulfate in 0.5 ml. water as described in Example XXII to yieldja viscous solution of-the polymer.

l oly'mer' of N-methyl methylsu'lfate of A- solutiou o f 16.2 g. of themonomeric' quaternary ammonium salt inj 37 of water was: treated with'a 0lution,.0f 0.16 g}; ammonium;persu1fate 1110.8 mLof water by the procedure described in Example The .'resultant :solution of; the: polymerwas. thick a d syrupy,

the acrylate ester .of ,B-diethylaminoethyl ether of ethylene glycol;'

asaaee't 9 Example XXXII Polymer of N-methyl methylsulfate of the methacrylate ester of ,B-dimethylaminoethyl ether of ethylene glycol.

A solution of 22.3 g. of the monomeric quaternary ammonium salt in 50 ml. water was treated with 0.2 g. ammonium persulfate dissolved in 4.4 ml. water as described in Example XXII. A viscous polymeric product was obtained.

Example XXXIH Polymer of N-methyl methylsulfate of the methacrylate ester of B-dibutylaminoethyl ether of ethylene glycol.

A solution of 12.7 g. of the monomeric quaterr ammonium salt in 29 ml. water was treated with a solution of 0.2 g. ammonium persulfate in 1 ml. water by the procedure described in Example )CGH. The resultant solution of the polymer was syrupy.

Example XXXIV Polymer of N-methyl methylsulfate of the methacrylate ester of [3(1-piperidino) ethyl ether of ethylene glycol.

A solution of 15 g. of the monomeric quaternary ammonium salt in 27 ml. water was treated with 0.15 g. ammonium persulfate in 3 ml. water by the procedure described in Example XXIII to give a viscous solution of the polymer.

The polymers of the present invention are of particular value as antistatic agents and the following example is directed to such use.

Example XXX V Polymer of N-methyl methylsulfate of the methacrylate ester of -dimethylamino propyl ether of diethylene glycol.

Nitrogen was passed through a solution of 29 g. of the quaternary ammonium compound in 71 ml. water containing .05 g. Topanol A. The solution was heated to 95 with stirring and 0.75 ml. of a 10% aqueous solution of ammonium persulfate was added. An exothermic reaction ensued and after maintaining the temp-erature at 95 or above for fifteen minutes a very viscous product was obtained.

Example XXXVI The aqueous solution of the polymeric N-methyl methylsulfate of the methacrylate ester of p-diethylaminoethyl ether of ethylene glycol of Example XXIII was diluted to give a /3 aqueous solution of the polymer and the solution heated to 60 C. Nylon (polymeric hexamethylene adipamide) ZOO-taifeta was padded with this solution. Pick-up was approximately 80%. The material was frame dried at 80 C. for 10 minutes and then rinsed with a 1% solution of sodium oleyl sulfate to retain slightly less of the sodium oleyl sulfate than of the polymer. The fabric was again frame dried at 80 C. to give a material which had superior antistatic properties and whose antistatic properties showed a high resistance to laundering.

The temperature of the padding, rinsing and drying operations are not critical.

In place of the nylon of Example XXXVI, there can be treated any other polymer subject to accumulations of static electricity. In place of the sodium oleyl sulfate of Example XXXVI, there can be employed any other anionic detergent, such as the soaps of fat and fatty acids and sulfate and sulfonate detergents previously set forth.

We claim:

1. A compound having the formula:

wherein R is selected from the group consisting of hydrogen and methyl, R and R are selected from the group consisting of (a) alkyl groups having 1 to 4 carbon atoms and (b) are joined together to form with the nitrogen atom a heterocyclic ring selected from the group consisting of $15: $H1 (1H3 (1H2 CH; on, and CH: CH:

l l R, is selected from the group consisting of methyl and ethyl, n is an integer from 1 to 5 inclusive, 2 is an integer from 2 to 4 inclusive and X is an anion.

2. Polymers of the compounds of claim 1.

3. The salt of an acid with the trialkyl aminoalkylene ether of an ethylene glycol ester of methacrylic acid, two of said alkyl groups having up to 4 carbon atoms and the third alkyl group having up to two carbon atoms, said ethylene glycol group having up to 5 ethylene oxide units.

4. Polymers of the compounds of claim 3.

5. The salt of an acid with the trialkylaminoalkylene ether of an ethylene glycol ester of acrylic acid, two of said alkyl groups having up to 4 carbon atoms and the third alkyl group having up to two carbon atoms, said ethylene glycol group having up to 5 ethylene oxide units.

6. Polymers of the compounds of claim 5.

7. N-methyl methyl sulfate of the methacrylate ester of ,B-diethylaminoethyl ether of ethylene glycol.

8. N-methyl P-toluenesulfonate of the methacrylate ester of B-diethylaminoethyl ether of ethylene glycol.

9. N-methyl methyl sulfate of the methacrylate ester of fi-diethylaminoethyl ether of triethylene glycol.

10. N-methyl methyl sulfate of the acrylate ester of diethylaminoethyl ether of ethylene glycol.

11. A polymer of the compound of claim 7.

12. A polymer of the compound of claim 8.

13. A polymer of the compound of claim 9.

14. A polymer of the compound of claim 10.

15. A compound according to claim 1, in which the anion is a sulfonate ion.

16. A compound according to claim 1, in which the anion is a sulfate ion.

References Cited in the file of this patent UNITED STATES PATENTS 2,138,763 Graves Nov. 29, 1938 2,693,430 Cross Nov. 2, 1954 2,694,688 Hughes Nov. 16, 1954 2,723,246 Boyd Nov. 8, 1955 

1. A COMPOUND HAVING THE FORMULA: 